CN102906233A - Process for selective oxidation of carbon monoxide - Google Patents
Process for selective oxidation of carbon monoxide Download PDFInfo
- Publication number
- CN102906233A CN102906233A CN2011800267977A CN201180026797A CN102906233A CN 102906233 A CN102906233 A CN 102906233A CN 2011800267977 A CN2011800267977 A CN 2011800267977A CN 201180026797 A CN201180026797 A CN 201180026797A CN 102906233 A CN102906233 A CN 102906233A
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- China
- Prior art keywords
- hydrocarbon
- carbon monoxide
- catalyzer
- oxidation
- gas
- Prior art date
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- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 78
- 230000003647 oxidation Effects 0.000 title claims abstract description 74
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 50
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 39
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- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
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- C01B32/50—Carbon dioxide
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
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- C07C7/00—Purification; Separation; Use of additives
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- C07C7/14833—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with metals or their inorganic compounds
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- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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- C10L3/104—Carbon dioxide
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- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a process for the selective oxidation of carbon monoxide to carbon dioxide present in a gas mixture comprising at least one hydrocarbon or a hydrocarbon derivative, and to its integration into a process for producing hydrocarbon derivatives. The process according to the invention comprises a step that consists in bringing said gas mixture into contact with a solid catalyst capable of oxidizing carbon monoxide to carbon dioxide at a chosen temperature, characterized in that said step is carried out in a fluidized bed.
Description
Invention field
Relate generally to of the present invention is made the field of hydrocarbon derivative by hydrocarbon in the presence of oxygen or oxygen containing gas in gas phase.The present invention more specifically relates to the co selective oxidation that exists and produces the method for carbonic acid gas in the gaseous mixture that comprises at least a hydrocarbon or hydrocarbon derivative, and relates in its method that is incorporated into the manufacturing hydrocarbon derivative.
Prior art and technical problem
Industrial by suitable hydrocarbon in gas phase at molecular oxygen or comprise in the presence of the gas of molecular oxygen and the partial oxidation in the presence of suitable catalyzer is made many hydrocarbon derivatives.
For example, acrylic acid main manufacture methods is based on the oxidation of propylene and/or propane.Oxidation acrylic acid synthesizing by propylene comprises two steps; First step is intended to propylene oxidation is produced propenal, and second step is intended to acrolein oxidation is produced vinylformic acid.This synthetic specific two kinds of catalyst system of each oxidation step that usually use in two reactors carry out, and these two steps are carried out in the presence of oxygen or oxygen-containing gas.
In the same manner, make Methylacrylaldehyde and methacrylic acid at industrial catalyzed oxidation by iso-butylene and/or the trimethyl carbinol.
Can pass through aromatic hydrocarbons, such as benzene or o-Xylol, or straight chain hydrocarbon, make acid anhydride such as the catalyzed oxidation of normal butane or butylene, such as maleic anhydride or Tetra hydro Phthalic anhydride.
By propylene or propane in gas phase in the presence of ammonia by air catalytic oxidation, make vinyl cyanide, this reaction is known as " ammonia oxidation ".Similarly, the ammonia oxidation of Trimethylmethane/iso-butylene or vinyl toluene produces respectively methacrylonitrile and atroponitrile (atroponitrile).
For economic reasons, these different methods at molecular oxygen or comprise in the presence of the gas of molecular oxygen, carry out in the presence of air in gas phase usually.Side reaction also occurs in the catalytic oxidation process, comprise the final oxidizing reaction of reactant, to cause forming oxycarbide and water.
Therefore, these different methods by selective oxidation manufacturing hydrocarbon derivative have the following fact jointly: they cause the formation oxycarbide---carbon monoxide CO and carbonic acid gas CO
2Usually with respect to CO
2Excessive generation carbon monoxide CO.They are uncondensable gaseous compounds under the temperature and pressure condition of commonly using in the recovery/purification step of hydrocarbon derivative.Therefore, they are discharged in the atmosphere to be used for the incineration discharge outlet form of the material that is removed stream in the method process, and shortcoming is a large amount of CO
2Be discharged in the atmosphere.
As in the most industry method, for productivity and profitability obvious reason, make some gas fractions that generate in the hydrocarbon derivative manufacturing processed, the gas fraction recirculation that particularly comprises unreacting hydrocarbon is favourable.In the situation that have carbon monoxide in these recycle gas, there is this not condensable compound in the method process, to gather and cause the danger of safety problem, particularly loses the danger to the control of oxidizing reaction and blast (carbon monoxide is flammable) in oxidation reactor.In addition, carbon monoxide can have deleterious effect to oxide catalyst; It is many catalyzer particularly, comprise the poisonous substance that makes propylene oxidation produce the traditional catalyst that propenal uses.
The a solution that overcomes these shortcomings is provided in document EP 484 136, the document has been described the manufacture method of hydrocarbon derivative, comprise make available from the gas stream of this reaction from this gas stream, extract in succession or separate the hydrocarbon derivative of expection, the CO that exists in this gas stream changes into CO
2Extract subsequently the CO that a part forms
2Rear recirculation.Therefore this recirculation flow is poor CO and CO
2Material stream.The oxidizing reaction of hydrocarbon is high enough to prevent from forming in this system in the presence of the inert diluent of fuel mixture, particularly at CO at content
2Carry out under existing.The CO selective oxidation becomes CO
2With catalyzer to be selected from for the unreacting hydrocarbon that exists in this gas stream be non-oxide catalyzer, be generally based on optionally supported on silicon-dioxide or aluminum oxide copper/manganese or the catalyzer of platinum/nickel mixed oxide.The example that illustrates this method is implemented with the CO convertor that comprises stationary catalyst bed.With regard to made acrylic acid by propylene with regard to, this test shows that 80% CO transforming degree and a part of propylene and propane are converted, and cause the loss of reactant thus in the method.
Another solution that overcomes these shortcomings is provided in document EP 1 007 499, and the document relates to the high yield method of being made maleic anhydride by normal butane, comprises that discharging a part of recycle gas gathers to prevent rare gas element and oxycarbide, and can be with O
2/ CO mol ratio is that the CO selective oxidation in 0.5 to 3 the gas becomes CO
2Catalyzer exist and lower the co selective oxidation that exists in this discharging current to be become carbonic acid gas.Can be used in this case the CO selective oxidation is become CO
2Catalyzer for example by the precious metal of load, consist of such as platinum, rhodium, ruthenium or palladium.The CO convertor is preferably fixed bed tubular type type.
Document EP 1 434 833 is provided at the catalyzer substrate on the almost continuous coated silica supports of the material that is made of molecular sieve, such as Pt, Pd, Pt-Fe or Pd-Fe as in comprising the gas stream of at least a alkane, the CO selective oxidation being become CO
2With catalyzer.In fixed bed, make this catalyzer carry out the selective oxidation of CO under to the selected temperature of alkane without any effect.
That describes in document EP 495 504 is made in the method for methacrylic acid by Trimethylmethane, comprise the condensable fractions of methacrylic acid in separation after, use the CO oxidation that in can not condensing gas stream, exists to change into CO
2Step, then by in comprising the liquid of the solution of salt of wormwood and amine for example, absorbing with carbonic anhydride isolated in form CO
2Step.Can be used for CO and change into CO
2(without the oxidation of Trimethylmethane) catalyzer for example is included in palladium and/or platinum, the gold on carrier or the manganese oxide on the carrier.In order to remove the heat of oxidizing reaction, multi-tubular reactor is as this CO convertor.
In these different methods of prior art, at low-speed SV(usually less than 10 000 h
-1) (air speed is defined as the ratio of reactant flow and catalyst volume, or the inverse of " duration of contact ") is lower or carry out the CO selective oxidation become CO under the low CO concentration of ingress
2Transform when in some cases, it also causes the hydrocarbon that exists in this gas.
Because the flammability hazard that is associated with the existence of hydrocarbon and oxygen is made the method for hydrocarbon derivative and is usually used low hydrocarbon content to move so that gaseous reaction mixture remains on outside the flammable range by the catalyzed oxidation of hydrocarbon in gas phase.
In order when observing safe limit, to improve the productivity of these methods, can in the presence of rare gas element, (be also referred to as quality thermal capacitance Cp with high specific heat, index p refers to the value under constant voltage) carry out the oxidizing reaction of hydrocarbon, with the better management and the hydrocarbon concentration of raising in reaction mixture that obtain this exothermic heat of reaction, this rare gas element consists of heat town thing (ballast thermique).
Therefore, document EP 293 224 proposes the saturated aliphatic hydrocarbon with 1 to 5 carbon atom of 5 to 70 volume %, add in the propylene oxidation reaction such as methane, ethane or propane, this reaction produces propenal in make acrylic acid two step methods by catalyzed oxidation, second step is acrolein oxidation is become vinylformic acid.
As the hydrocarbon that can be used as the heat town thing in the method, propane is preferred.This be because, this gas ballasting thing with by rare gas element, the gas ballasting phase ratio that forms such as nitrogen or carbonic acid gas shows some advantages.At first, it provides better heat town thing, because its specific heat (Cp) greatly improves with temperature, in the situation that nitrogen is really not so.In addition, it has certain unreactiveness under the condition of carrying out the propylene oxidation reaction, and its possible reaction product is in close proximity to the reaction product of propylene in itself.At last, it more easily satisfies the base composition condition of this mixture relevant with flammability issues by reaction mixture is in more than the upper limit of flammability.Owing to using this heat town thing, the volume fraction of raw material that is supplied to the reactor of propylene oxidation can be larger, and this improves and transforms productivity, controls simultaneously the focus in the catalyst bed and promote thus the selectivity of reaction.
Using heat town thing, in the situation such as propane, because the cost of propane more requires to make the material stream recirculation that comprises unreacted propylene (and propane), therefore more difficult selectivity is rich in the oxidation of the carbon monoxide in the material stream of hydrocarbon mixture.
The problem that the present invention wants to solve is in being rich in the material stream of hydrocarbon or hydrocarbon mixture CO to be changed into CO
2, but these hydrocarbon of not oxidation.The selective conversion of CO insulation fix bed or even have in the multi-tubular reactor of good heat exchange and can begin, but can produce fast this runaway reaction (emballement), this greatly improves the temperature of catalyzer and other compound that exists in this material stream is transformed.In fact, in fixed-bed reactor, the conversion that existing a large amount of CO cause adiabatic heating consequently to surpass all the components begins temperature (ignition temperature).
CO changes into CO
2The exothermicity of reaction take the Hr of 283 kJ/mol as feature.Even the exothermicity of the selective oxidation reaction of hydrocarbon is suitable, for example to change into the Hr of propenal be 341 kJ/mol to propylene, and the kinetics of this combustion reactions is also faster.At this moment " tradition " technology of multi-tubular reactor type does not allow correctly to control the temperature of catalyzer.Under the controlled condition of temperature, can under than the lower temperature of the oxidizing temperature of hydrocarbon, CO be changed into CO
2, so it can selectivity carry out.
Because the ignition temperature between the various compositions that exist in CO and the hydrocarbon flow is poor significantly, the CO selective oxidation can be become CO in theory
2, as long as temperature of reaction remains between the ignition temperature of the ignition temperature of CO and other composition.
As indication, the raising of gas temperature is presented in the following table 1 in the combustion processes of 1000 ppm impurity in air.
Table 1.
Be rich in specific heat and be higher than the gas of air specific heat, in the atmosphere such as propane, the raising of adiabatic temperature is lower pro rata.
Under this background, applicant company has been found that in being rich in the material stream of hydrocarbon and uses fluidized-bed that CO is changed into CO
2Can solve above-mentioned variety of issue and satisfy best and make in the method for hydrocarbon derivative by hydrocarbon selective oxidation in the presence of oxygen in gas phase, be more typically in by hydrocarbon and in gas phase, in the presence of oxygen, use the hot requirement that presses down thing and/or comprise the reactant gases recirculation of too high CO content in the method for manufacturing hydrocarbon derivative.
The CO oxidation of use fluidized-bed has consisted of the object of research, comprises Pt-Co-Ce/ γ-Al especially for research
2O
3The impact of the conversion of the CO that exists in the gas stream of the structure of the reactor of the special catalyst of type on rich hydrogen (people such as M.P. Lobera, Catalysis Today, 157 (2010), 404-409).In this research, the material stream of processing is only hydrogeneous, so that does not mention complex mixture, such as the selective oxidation problem of the CO in the hydrocarbon mixture (should avoid its oxidation).
Therefore purpose of the present invention provides the method that co selective oxidation is become carbonic acid gas, and it easily is integrated in the existing commercial run for the manufacture of hydrocarbon derivative.
Summary of the invention
Therefore a theme of the present invention is the process for selective oxidation of the carbon monoxide that exists in the gaseous mixture that comprises at least a hydrocarbon or hydrocarbon derivative, described method comprises makes described gaseous mixture and the step that the solid catalyst that can Oxidation of Carbon Monoxide be become carbonic acid gas under selected temperature contacts, and it is characterized in that described step carries out in fluidized-bed.
This fluidization provides mixing of this solid and gaseous mixture and the therefore homogenizing of catalyst temperature.By obtaining uniform temperature, therefore can control the selectivity of Oxidation of Carbon Monoxide reaction and no longer destroy can value-added molecule.This homogeneity is given fluidized-bed and is compared undeniable advantage with the fixed bed that usually stands high-temperature gradient.Can provide removing of reaction heat by the cooling pin (é pingles de refroidissement) that is arranged in the fluidized-bed.Heat transfer coefficient between this suspension and the exchanging tube is very high and can effectively heat or cool off this material.
CO process for selective oxidation of the present invention can be integrated into for chemical principle and require to discharge CO because of (inhibition of reaction), physical cause (reduction of the Cp of reactant gases) or security reason (flammable limit)
2And/or in any commercial run of CO.
Another theme of the present invention is the manufacture method of hydrocarbon derivative, comprises that at least one use comprises the step that the fluidized-bed selective oxidation that can Oxidation of Carbon Monoxide be become the solid catalyst of carbonic acid gas under selected temperature comprises the carbon monoxide that exists in the gaseous mixture of at least a hydrocarbon or hydrocarbon derivative.
Clearlyer when reading following detailed description and non-limiting example of the present invention find out other features and advantages of the present invention.
Describe in detail
The gaseous mixture that stands CO process for selective oxidation of the present invention comprises at least a hydrocarbon or hydrocarbon derivative.
This hydrocarbon is to comprise the saturated of 2 to 6 carbon atoms or single-or the hydrocarbon of two undersaturated straight or brancheds, or comprise 6 to 12 carbon atoms can substituted aromatic hydrocarbons.
As the example of hydrocarbon, can mention for example ethene, propane, propylene, normal butane, Trimethylmethane, iso-butylene, butylene, divinyl, isopentene, benzene, o-Xylol, vinyl toluene, naphthalene.This hydrocarbon is preferably selected from separately or as propylene or the propane of mixture.
This hydrocarbon derivative can be the product of the partial oxidation of hydrocarbon, at this moment it can be selected from acid anhydride, such as Tetra hydro Phthalic anhydride or maleic anhydride, aldehyde is such as propenal or Methylacrylaldehyde, unsaturated carboxylic acid, such as acrylic or methacrylic acid, unsaturated nitrile, such as vinyl cyanide, methacrylonitrile or atroponitrile, or their mixture.This hydrocarbon derivative is propenal and/or vinylformic acid preferably.
This hydrocarbon derivative also can be that oxygen or halogen compounds add to the product on the unsaturated hydrocarbons, for example oxyethane, propylene oxide or 1,2-ethylene dichloride.
As the solid catalyst that Oxidation of Carbon Monoxide can be become carbonic acid gas available in the method for the present invention, can mention the known catalysts for the selective oxidation of CO, for example, but be not limited to, based on loading on inorganic carrier, such as the precious metal on silicon-dioxide, titanium oxide, zirconium white, aluminum oxide or the silica, such as the catalyzer of platinum, palladium, rhodium or ruthenium; Or based on copper, manganese, cobalt, nickel or iron, with the optional at least a precious metal that exists, such as platinum, palladium, rhodium or ruthenium, for optionally supported at inorganic carrier, such as the catalyzer of the form of the mixed oxide on silicon-dioxide, titanium oxide or zirconium white, aluminum oxide or the silica or alloy.Most suitable catalyzer is the solid that for example has low platinum or palladium carrying capacity (for example about 2%) at the carrier of silica or type of sodium silicates.
Used catalyzer is that granularity is 20 to 1000 microns in the method for the present invention, preferred 40 to 500 microns, and 60 to 200 microns solids form more especially.According to many methods, can measure especially the size-grade distribution of particle according to simple method, a succession of sieve screening of for example successively decreasing with sieve mesh, or for example pass through determination of laser diffraction with the Malvern board apparatus.
According to the present invention, the temperature of fluidized-bed is 20 ℃ to 400 ℃, preferred 70 ℃ to 300 ℃, and more preferably 100 ℃ to 230 ℃.
Preferably, select than the hydrocarbon that exists in this gaseous mixture and/or hydrocarbon derivative " temperature that the ignition in hydriding temperature is low namely is lower than corresponding temperature when initial with the oxidizing reaction of hydrocarbon and/or hydrocarbon derivative.
For example, in the situation that propylene, there are about at least 20 ℃ usually between CO ignition temperature (CO burn beginning) and the propylene ignition temperature, preferably at least 30 ℃ of differences.This difference sufficient to guarantee CO burns and does not have the propylene burning.If reach the ignition temperature of propylene, because hyperoxia and the propylene content of gas to be processed, this reaction becomes and is difficult to control.
This fluidized-bed can discontinuous (in batches) or continuously (semi-batch or opening) mode move.Method of the present invention is preferably carried out continuously.This be because, consider in its operational process and easily from fluidized-bed, to extract solids and solids are added in the fluidized-bed, can replace continuously on demand solid phase.If extract continuously the catalyzer of inactivation to change it into live catalyst, this catalyst bed is the activity through remaining unchanged in time.Just as water receptacle, the emptying and cleaning of fluidized-bed is very easy to carry out.This extraction operation can be carried out continuously or with some cycles.In addition, the catalyzer of this inactivation can be chosen wantonly by any suitable technology ex situ reactivate, in the reactor that reinjects subsequently.As the reactivation of catalyst technology, can mention, but be not limited to, the metal by pulverization process redispersion catalyzer, washing catalyst to be removing pollutent, or flood this catalyzer with the fresh feed of catalyst activity metal again.
Can be with reference to the document about fluidization technique among Techniques de l ' the Ing é nieur J3 390 1 to 20.
Advantageously, use the mild oxidation condition, the combination of the catalyzer of namely relatively little activity (reactive metal that comprises low carrying capacity), moderate temperature (for example 80 ℃ to 180 ℃) and quite short duration of contact (for example less than 1 second).Perhaps, the low residence time allows for given catalyzer and uses comparatively high temps.
Advantageously, in fluidized-bed reactor example such as the middle pressure of 1 to 3 bar and the quite short residence time (being presented as high-speed).Need in the situation of elevated pressures in the condition relevant with this technique, at this moment preferably the catalyzer of relatively little activity is combined to limit the oxidizing reaction of other composition of this gas stream with alap temperature.
The linear speed of gaseous mixture in fluidized-bed can be 0.1 to 80 cm/s.For the fluidized-bed of industrial size, it can be 50 to 80 cm/s.In the situation of the fluidized-bed of lower height, particularly in the situation of laboratory fluidized-bed, the linear speed of gas is generally 0.1 to 10 cm/s most.
Therefore usually, according to catalyst volume with according to the volumetric flow rate of reactor size adjustments of gas stream, represent with hour volumetric flow rate with respect to the reactant of catalyst volume to realize very high air speed SVs().
Method of the present invention is advantageously with for example 1000 h
-1To 30 000 h
-1, be preferably greater than 10 000 h
-1Or 10 000 h better
-1To 30 000 h
-1High-speed SVs carry out.Method of the present invention is specially adapted to comprise more than 0.5 % by mole of carbon monoxide in the ingress, preferably more than the gas stream of 1 % by mole of carbon monoxide.
Another theme of the present invention is the manufacture method of hydrocarbon derivative, and it comprises at least the following step:
A) at least a hydrocarbon and oxygen or oxygen-containing gas are contacted with suitable catalyzer, comprise the gaseous mixture of at least a hydrocarbon derivative, unconverted hydrocarbon, oxygen and carbon monoxide with generation,
B) from from separating step reaction stream a) or extract hydrocarbon derivative,
C) then use to be included in and Oxidation of Carbon Monoxide can be become the fluidized-bed of the solid catalyst of carbonic acid gas that the carbon monoxide that exists in this gas stream is changed into carbonic acid gas under the selected temperature, producing the gas stream of poor carbon monoxide,
D) gas stream with described poor carbon monoxide is recycled to reactions steps a).
Will be clear that to be understood that, this method can comprise well known to a person skilled in the art before the step mentioned above, among and/or afterwards other step.
The method according to this invention, step particularly relates under catalyst property, temperature and the condition as the optional existence of the rare gas element of heat town thing and carrying out a) according to the method that can make required hydrocarbon derivative well known by persons skilled in the art under proper condition.
The reaction of carrying out can be oxidizing reaction or oxygen added to reaction on the unsaturated hydrocarbons.
In another form of the present invention, step a) is carried out in the presence of heat town thing, and described heat town thing is inertia under the condition of the reaction of carrying out.
Step b) be to use according to conventional methods as in solvent, absorb, then extract, the technology of distillation, crystallization, condensation reclaims hydrocarbon derivative.
At this step b) when finishing, make the gas stream that has removed most of hydrocarbon derivative (usually comprise unconverted hydrocarbon, oxygen, water vapor, rare gas element, such as nitrogen and argon gas, carbon monoxide and carbonic acid gas) in fluidized-bed with can under selected temperature, Oxidation of Carbon Monoxide be become the solid catalyst of carbonic acid gas contact (step c)), to produce the gas stream of poor carbon monoxide, it can be chosen wantonly behind the carbonic acid gas of therefrom discharging part formation according to steps d) be recycled to reactions steps a).
In a specific embodiments of the present invention, comprise and use fluidized-bed that the CO partial oxygen is changed into CO
2Step c) the hydrocarbon derivative manufacture method relate to by making vinylformic acid at propane as the propylene catalyzed oxidation in the presence of the heat town thing with oxygen or oxygen-containing mixture.
The industrial this reaction of extensively carrying out is carried out in two steps gas phase neutralization is the most common usually:
First step carry out propylene almost quantitatively oxidation is to produce the mixture of rich propenal, wherein vinylformic acid is accessory constituent, then carries out the selective oxidation of propenal to produce vinylformic acid in the second step process.
In two reactors of series connection or comprising the catalyzer of different and suitable this reaction of needs of the reaction conditions of these two steps of carrying out in the single reactor of 2 reactions steps of series connection; But, in this two step method processes, needn't separate the first step propenal.
Can for this reactor supply low-purity propylene feedstocks, namely comprise propane, so that the propane/propylene volume ratio equals 1 at least.Because the large air heat town thing that is formed by propane causes the better management to exothermic heat of reaction, can supply the more raw material of enrichment propylene for this reactor, with the productivity of raising the method.Other component of reacting material flow can be inert compound, such as nitrogen or argon gas, and water and oxygen.
Gaseous mixture available from the acrolein oxidation reaction also comprises except vinylformic acid:
-uncondensable light compounds under temperature and pressure condition commonly used: nitrogen, unconverted oxygen and unconverted propylene, propane, carbon monoxide and the carbonic acid gas (they are in the method by final oxidation or a small amount of formation of circulation circulation (by recirculation)) that are present in the propylene or add as heat town thing
-condensable light compounds: the water, unconverted propenal, the light aldehyde that particularly generate by the propylene oxidation reaction, such as formaldehyde and acetaldehyde, acid, such as acetic acid, the major impurity that in conversion zone, generates,
-heavy compounds: furfural, phenyl aldehyde, toxilic acid and maleic anhydride, phenylformic acid, 2-butylene acid, phenol etc.
Step b with method of the present invention) the second corresponding manufacturing stage is to be recovered in the vinylformic acid that exists in the gaseous emission available from oxidizing reaction.
This step can absorb by convection current carries out.For this reason, introduce the gas of autoreactor in the bottom, absorption tower, the solvent of introducing at cat head is met in its convection current herein.Remove in temperature and pressure condition commonly used (respectively greater than 50 ℃ with less than 2 * 10 at the top on this absorption tower
5Pa) light compounds under.Used solvent is water in this tower.Water can be as substituting being had high boiling hydrophobic solvent described in for example BASF patent FR 2 146 386 or US 5 426 221 and the patent FR 96/14397.
The operational condition of this absorption step is as follows:
Under 130 ℃ to 250 ℃ temperature, introducing this gaseous reaction mixture at the bottom of the tower.Under 10 ℃ to 60 ℃ temperature, introduce water at cat head.Water and gaseous reaction mixture amount separately is so that water/vinylformic acid weight ratio is 1/1 to 1/4.Under atmospheric pressure carry out this operation.
Obtain to remove thus most of unconverted propenal and light compounds, the aqueous mixture (weight ratio be 1/1 to 4/1) of vinylformic acid in water that particularly can not condensed light compound (comprising CO), this mixture is commonly referred to as " rough vinylformic acid ".
Subsequently this rough vinylformic acid is imposed the combination of step, the order of step can be according to method and difference: except anhydrating and the dehydration (dehydration vinylformic acid) of formaldehyde, remove lighter products (particularly acetic acid), remove heavy product, optionally remove some impurity by chemical treatment.
Use from by the acrylic acid previous step of convection current absorption extraction gas stream---it is mainly by unconverted propylene, unconverted oxygen, propane, CO and CO
2Consist of with other less important rare gas element or light impurities---in fluidized-bed with can under selected temperature, become the solid catalyst of carbonic acid gas to contact Oxidation of Carbon Monoxide, to produce the material stream of poor carbon monoxide, it can be recycled to reactions steps behind the optional carbonic acid gas of therefrom discharging part formation.
In a modification of method of the present invention, will come from all or part of gas stream for the unit that carbon monoxide is changed into carbonic acid gas and be sent to the selective permeation unit and mainly comprise inert compound to separate, such as CO, CO
2, nitrogen and/or argon gas the first material stream, and mainly comprise the second material stream of propylene and propane.This permeation unit uses one or more semi-permeable membraness with ability that inert compound is separated with hydrocarbon.This separation is usually at the pressure of about 10 bar with carry out under about 50 ℃ temperature.Can use the film based on the tubular fibre that is made of polymkeric substance, described polymkeric substance is selected from: the multipolymer of the polymkeric substance of polyimide, derivatived cellulose type, polysulfones, polymeric amide, polyester, polyethers, polyetherketone, polyetherimide, polyethylene, polyacetylene, polyethersulfone, polysiloxane, poly(vinylidene fluoride), polybenzimidazole, polybenzoxazole, polyacrylonitrile, poly-azo aromatic substance and these polymkeric substance.
Described the second material stream that is rich in propylene and propane advantageously is recycled to reactions steps, and does not have CO
2With other rare gas element, accumulate in the recirculation loop such as argon gas.
In second modification of method of the present invention, all or part of gas stream that enters for the unit that carbon monoxide is changed into carbonic acid gas is sent to aforesaid selective permeation unit in advance, to separate at least a portion CO
2, at this moment the gas stream that enters the CO convertor removes CO
2With unconverted oxygen.
In following experimental section, easily find out other features and advantages of the present invention.
Experimental section
Embodiment 1
Be that 25.4 millimeters and catalyzer height are to use catalyzer from Johnson Matthey (at CeO in the reactor with molten salt bath of 30 centimetres (i.e. 164 grams) at internal diameter
2Upper 2% Pt) carries out the oxidation test of pure compound.
This test is the conversion (each composition is wherein tested in conversion test one by one) of monitoring pure compound in the mixture of nitrogen and oxygen (3 % by mole).For some tests, change a part of nitrogen into water (20 % by mole).At 25 000 h
-1The SV condition under the following concentration of test (representative is to the desired concentration value rank of each compound in the actual material stream), measure the conversion of this compound as temperature function:
-CO:2.8 % by mole
-propylene: 0.75 % by mole
-propenal: 0.75 % by mole
-propane: 50 % by mole
-optional water.
These conditions be equivalent to propylene at propane as the oxidizing condition in the presence of the heat town thing.
Respectively in the situation that have water and do not have water, be reproduced among Fig. 1 and 2 as the variation of the pure compound oxidation of the function of temperature.In Fig. 1, the CO transformation efficiency under 180 ℃ be 100% and propylene oxidation under 235 ℃, obviously begin.In Fig. 2, curve 1 is corresponding to propenal, and curve 2 is corresponding to CO, and curve 3 is corresponding to propylene.
Begin with the oxidizing reaction of pure compound that corresponding " the ignition in hydriding temperature collects in the following table 2.In this table, institute's temp. displaying function is equivalent to reactor but not the temperature that applies to catalyzer.
| Compound | CO | Propylene | Propenal | Propane |
| Ignition temperature when anhydrous | 225℃ | 265℃ | 285℃ | ? |
| Ignition temperature when having water | <?180℃ | 235℃ | ? | >?300℃ |
Table 2
Use pure compound, the ignition temperature of reaction is different (differences〉30 ℃) obviously, show to be conducive to fully evacuate energy so that temperature of reaction remains under the good temperature of selectivity wherein.
Embodiment 2(contrast)
With catalyst fixed bed and with following concentration inclusion compound CO, CO
2, propane, propylene, propenal, water and oxygen the material stream of mixture reproduce embodiment 1, wherein wish the CO selective oxidation is become CO
2:
-CO:2.8 % by mole
-propylene: 0.75 % by mole
-propenal: 0.75 % by mole
-water: 20 % by mole
-oxygen: 3 % by mole
-propane: 50 % by mole.
The test of carrying out shows, in the presence of the mixture of compound, as long as can supply oxygen, observes the perfect combustion of reactant with following reactive order:
CO〉propylene〉propenal〉propane.
Temperature is not controlled: can measure focus, the temperature that wherein reaches in the catalytic bed is than at least 150 ℃ of furnace temperature height.Therefore, because this difference is much larger than the difference that records between the ignition temperature of pure substance, all oxidizing reactions are upset simultaneously, improve whole exothermicity largelyr.Only find that oxidizing reaction just slows down when oxygen depletion.
Catalyzer is diluted 90 % by weight to reproduce this test with inert material (from the alumina/silica bead of Saint-Gobain).The dilution of catalyzer has the catalytic activity of reduction reactor with the purpose of better red-tape operati temperature range.Therefore, the catalyzer+inert material of reciprocity volume, the 10 % by weight primary catalyst of in reactor, packing into and 90 % by weight inert materials.Purpose also has the heat of disperseing to come automatic oxidation reaction at larger reaction volume.By conducting heat through wall, remove the heat from this reaction; Inert solid provides the greater amount point of contact and should be able to better control thus temperature in the catalytic bed between catalyzer and wall.Although catalyzer high dilution (being equivalent to the strong raising of air speed), the temperature head between the focus of catalytic bed and the furnace temperature (or ignition temperature of CO oxidizing reaction) is still poor greater than the ignition temperature of CO and propylene.
Under these conditions, oxidizing reaction is not always controlled, can not address this problem with inert material (90 % by weight) dilute catalyst.Still, also face not fit between catalyzer and the reactor used technology.
Embodiment 3: be used for the preparation of the catalyzer of co selective oxidation
The preparation of catalyst A
By the porous silica spheres body of just wet impregnation method (impregnation à humidit é naissante) with 80 microns of the solution impregnation 200 gram diameters that comprise 10.2 gram citric acids, 20.2 gram hydrogen-carbonates, four ammonia platinum (II) (comprising 50.6% platinum), 8 gram Fe(NO3)39H2Os (III) and 103.5 gram softening waters.Under agitation use mild heat with the evaporation excessive water, this solid keeps rotation to prevent agglomeration in rotary oven simultaneously.At last, then this powder was calcined 2 hours under 500 ℃ under air 105 ℃ of lower dryings.
The preparation of catalyst B
By flooding the Puralox SCCA 5-150 aluminum oxide from Sasol according to follow procedure, Kaolinite Preparation of Catalyst:
Introduce 300 gram aluminum oxide in 3 liters of jacketed reactors being heated to 100 ℃ and with air purge with the fluidisation aluminum oxide.Then use pump to inject continuously the solution of 15.3 gram citric acids, 30.3 gram hydrogen-carbonates, four ammonia platinum (II) (comprising 50.6% platinum), 12 gram Fe(NO3)39H2Os and 155 gram softening waters.Target rate (weight metal/final catalyst weight) is 0.5 % by weight Pt-0.5 % by weight Fe, and the interpolation time length of this solution is 2 hours.Catalyzer was kept 16 hours, then 500 ℃ of lower calcinings 2 hours in baking oven under 105 ℃.
This aluminum oxide has median diameter when beginning be about 85 microns particle, and have lower presentation surface and porosity characteristics:
BET surface-area (m
2/ g) 148
Hg total pore size volume (cm
3/ g) 0.87
D50: 50% apparent mean diameter of population: 85 μ m
Porosity peak value (nanometer): 9.
Embodiment 4
Reproduce embodiment 2, but use fluidized-bed.
In fluidized-bed, use catalyst A and B, have the composition of describing in the following table 3 and be preheated to 100 ℃ material stream to this fluidized-bed supply.This material stream is realized the fluidisation of catalyzer.Total pressure in the reactor is 2.2 bar, and the linear speed of gas is 10 cels.
| Mole forms | % |
| Acetaldehyde | 0.11% |
| Propenal | 0.24% |
| H 2O | 2.43% |
| O 2 | 10.26% |
| Argon gas | 1.99% |
| CO | 3.95% |
| CO 2 | 23.90% |
| Propane | 53.87% |
| Propylene | 1.67% |
| Acetic acid | 0.00% |
| Vinylformic acid | 0.01% |
| Nitrogen | 1.56% |
| ? | ? |
| Pressure (bar) | 2.2 |
| Temperature (℃) | 40 |
Table 3
After collecting product and make water condensation, reactor outlet passes through chromatography analysis.
Acquired results is presented in the following table 4:
| Catalyzer | CO transformation efficiency (%) | Propylene conversion (%) | Acrolein conversion rate (%) | Conversion of propane (%) |
| A | 90 | 5 | 3 | 1 |
| |
100 | 4 | 1 | nd |
Table 4
Catalyzer C, the D that the below defines and E obtain and are ground to the granularity less than 315 microns with particle form.This powder of screening 150 grams is to select the fraction between 80 to 160 microns.
Catalyzer C: from the ND-520 catalyzer of N.E. Chemcat, the Pt/ aluminum oxide, 3 millimeters bead form, density are 0.74 kg/l.
Catalyzer D: from DASH 220 catalyzer of N.E. Chemcat, 0.5% Pt/ aluminum oxide, 3.2 mm granules forms, specific surface area are 100 meters squared per gram
Catalyzer E: from the ND103 catalyzer of N.E. Chemcat, 0.5% Pd/ aluminum oxide, the bead form that diameter is 3 millimeters, 250 meters squared per gram.
150 gram solid catalysts are placed fluidized-bed.Fluidized-bed is made of 41 millimeters stainless steel tubes with 790 millimeters of total heights of diameter.This fluidized-bed is immersed in by in the fluidisation sand bath that is installed in the electrical element heating in bathing.Three thermopairs are along this pipe record thermograde.Below the expanded metal of the distribution of gas of crossing reactor diameter, with the flow velocity of 1760 ml/min (standard conditions), i.e. the gas linear speed supply of about 2.2 cm/s has the material stream of the mole composition of describing in the following table 5.
Total pressure in the fluidized-bed is 1 bar, and temperature remains on about 100 ℃.
| The mole that enters the gas of fluidized-bed forms | % |
| Acetaldehyde | 0.12% |
| Propenal | 0.31% |
| H 2O | 2.68% |
| O 2 | 4.39% |
| Argon gas | 1.95% |
| CO | 5.31% |
| CO 2 | 13.34% |
| Propane | 68.73% |
| Propylene | 1.93% |
| Acetic acid | 0.00% |
| Vinylformic acid | 0.01% |
| Nitrogen | 1.24% |
| ? | ? |
| Pressure (bar) | 1 |
| Temperature (℃) | 50 |
Table 5
After collecting product and make water condensation, the fluidized-bed outlet passes through liquid chromatography analysis.
Acquired results is presented in the following table 6:
| Catalyzer | CO transformation efficiency (%) | Propylene conversion (%) | Acrolein conversion rate (%) | Conversion of propane (%) |
| C | 82 | 3 | 1 | 0 |
| D | 90 | 4 | 1 | 0 |
| E | 65 | 3 | 1 | 0 |
Table 6
Embodiment 6: the preparation of catalyzer
Begun to carry out the test of three series by following catalyzer:
-0.5Pt catalyzer (is equivalent to 0.5%Pt and 0.5%Fe/ in aluminium oxide Al
2O
3On), volume density 0.78 g/ml, mean particle size 114 μ m.
-1.5Pt catalyzer (is equivalent to 1.5%Pt and 1.5%Fe/ in aluminium oxide Al
2O
3On), volume density 0.79 g/ml.
-2Pd catalyzer (being equivalent to 2% Pd/ on zeolite D/UR, from Engelhard/BASF), volume density 0.55 g/ml, mean particle size 144 μ m.
Front two kinds of catalyzer prepare according to following program, and the third catalyzer is the catalyzer that BASF sells.Latter's former state is used, and the particular modification except predrying not.
By the precursor (Pt and Fe salt) in the dissolving of Sasol aluminum oxide Puralox SCCA 5-150 dipping, for the preparation of the catalyzer of CO selective oxidation.
1) in first step, by the catalyzer of dipping for the preparation of the test of Micro Fluid bed that just wet.
Weigh up platinum and molysite and citric acid and in beaker, use water dissolution.By mixing 0.049 gram citric acid, 0.0987 gram hydrogen-carbonate, four ammonia platinum (II) (comprising 50.6% Pt), 0.36 gram nitric hydrate iron, 8.10 gram water and 9.9 gram aluminum oxide, preparation 0.5%Pt/0.5% Fe/ aluminium oxide catalyst.Calculate the total pore size volume (0.87 ml/g) of cumulative volume to equal carrier of this solution.In vigorous stirring, this solution is added in the carrier gradually subsequently.It is tied with carrier fully and is incorporated in the surface or can not detects liquid between particle.The gained thickener 110-120 ℃ lower dry 24 hours, then in air 485-520 ℃ of lower calcining 2 hours.
2) for the test in the larger reactor, use another technology, wherein in fluidized-bed, flood, aforesaid method is not suitable for 200 gram catalyzer, particularly for the homogeneity reason.Use following method to prepare 200 gram 0.5%Pt/0.5%Fe/Al
2O
3Use the precursor salt identical with above-mentioned preparation and identical concentration.
Place the cylindrical quartz pipe that is heated to 105-125 ℃ and with the carrier of Air Fluidized on dropwise supply the solution of precursor and citric acid.Calculate flow rate of liquid and remain on the 0.5-1 ml/min.Nozzle is positioned at about 10 centimeters in this top.Use air as fluidizing agent, regulate flow velocity to keep the ebullated bed state and to prevent the particle transported pneumatically.Thus obtained solid 120 ℃ lower dry 24 hours, then 500 ℃ of lower calcinings.
For the test in microreactor, use two kinds of charging levels (10 gram 1.5Pt/1.5%Fe/Al
2O
3With 10 gram 0.5Pt/0.5%Fe/Al
2O
3), for other test in larger reactor, only use a kind of charging level (200 gram 0.5Pt/0.5%Fe/Al
2O
3).
Embodiment 7: use the test of catalyzer in the fluidisation microreactor of embodiment 6
The microreactor that use is made of the silica tube of 7 millimeters of internal diameters is wherein serving as being positioned on the sintered glass (20 microns) in the middle part of this pipe of divider with 1 gram catalyst arrangement.Whole assembly is by computer control and can record all related experiment parameters (temperature, gas flow rate).
Under 40 ml/min, tested 15 minutes.This is equivalent to about 3000 h
-1Air speed SV.
Be supplied to gas composed as follows of the entrance of microreactor:
| Gas | Ar | O 2 | C 3H 6 | CO | CO 2 | C 3H 8 |
| % vol. | 5.53% | 7.61% | 1.69% | 5.19% | 10.6% | 66.79% |
Between these two tests, send into 40 ml/min argon gas with purge 10 minutes.Argon gas also is selected inert material in the heat-processed.
In order to understand the exothermicity of oxidizing reaction, furnace temperature is not carried out temperature control to the temperature of catalyst bed.For each experiment of carrying out, operational condition keeps constant at 15 minutes duration of test.
Gas by online spectrometer analysis reactor exit.
Fig. 3 provides and provides the composition of the rear exit gas of reaction and the temperature variation of catalytic bed as an example.All experiments of carrying out provide the have maintenance level graphic representation (profile) of same type of (niveaux stationnaire), calculate average conversion by these data.
The test of carrying out in microreactor is summarised in the following table 7.
N.d. represent non-availability
Table 7
Bold line is that wherein CO oxidation has been finished and is optionally experiment.
These tests show, the CO selective oxidation in this fluidized-bed is very effective, and transformation efficiency is 100% and do not have the oxidation of propylene and propane, and temperature is also fine controlled, because the intensification in the bed is extremely low.
Therefore can consider the CO selective oxidation in fluidized-bed under more on a large scale fully, as long as mild oxidation condition and good heat transfer are provided.Begun by the mathematical principle that uses kinetic constant, at this moment can determine fully will be with the optimum operation condition of technical scale use.
Embodiment 8: the test in the fluidized-bed reactor
Larger sized fluidized-bed can be tested with the catalytic amount that reaches 300 grams.Metallic reactors is divided into two sections: conversion zone (3.5 centimetres of diameters, 60 centimetres of height) and material discharge region (4.5 centimetres of diameters, 40 centimetres of height).Via flow regulator supply and adjustments of gas.These can realize the maximum volume flow velocity in this device of 4 liter/mins of clocks.Provide temperature control by the outside sand bath that the good temperature homogeneity in the reactor can be provided.Four temperature measuring points (two in catalytic bed, two in discharge zone) are installed in reactor.Also on outlet pipe mounted valve in order to reactor can be risen to required pressure.The aqueous acrolein solution that the pump of HPLC type is constant with flow velocity is directly introduced in the catalytic bed.
Online mass spectrograph can quantitative described product.The pipeline that is heated to 110 ℃ is connected to this assembly and thus any condensation of anti-sealing with mass spectrograph.The strainer prevention particle that is installed on the outlet pipe leaves reactor and prevents line clogging.
Test four kinds of different gas compositions and be summarised in the following table 8.Mark is done the test of E1 and is carried out under 2.2 bar absolute pressures, under atmospheric pressure carries out and mark the test of making E2.Each tests E1 or E2 " does " or " wetting " (in the presence of water vapor) carries out.
| In % | Ar | O 2 | C 3H 6 | CO | CO 2 | C 3H 8 | C 3H 4O | H 2O |
| E1 does | 3.8 | 11.3 | 1.7 | 4.4 | 23.9 | 54.9 | 0 | 0 |
| E1 is wet | 3.4 | 10.1 | 1.5 | 4.0 | 21.4 | 49.2 | 2.7 | 7.7 |
| E2 does | 3.2 | 4.5 | 1.8 | 5.5 | 14.0 | 71.0 | 0 | 0 |
| E2 is wet | 2.9 | 4.0 | 1.6 | 4.9 | 12.6 | 63.6 | 3.0 | 7.3 |
Table 8
Test at 150 gram 0.5Pt catalyzer according to embodiment 6 preparations.The volumetric flow rate that is used for test and is used for the gas of argon purge remain on about 600 ml/min reach 15 to 40 minutes (according to test with according to the stabilizing take of exit concentration) so that the active fluidization of particle to be provided.This represents about 180 h
-1Space-time speed.Because the minor diameter of reactor can not be in the situation that do not cause catalyst entrainment to use higher gas flow rate to operate to realize duration of contact and the larger space-time speed of much shorter.Yet these results represent such test, and those skilled in the art can infer that these tests when having larger sized device, use the more test of atmospheric linear speed and larger space-time speed.
Altogether calculating average conversion in the test period in 15-40 minute.
Be summarised in table 9 and 10 for the result in the test 1 of carrying out under 2.2 bar pressures and the test 2 under 1 bar pressure, carried out respectively.
Table 9: test 1 (2.2 bar)
Table 10: test 2 (1 bar).
The conditioned reaction time length is to realize the stable state of exit concentration.
Under 1 bar, even under the temperature more than 140 ℃, do not observe the conversion of propylene or propane yet.In addition, this intensification is very limited, shows the fabulous heat transfer in the fluidized-bed.
Claims (13)
1. the process for selective oxidation of the carbon monoxide that in the gaseous mixture that comprises at least a hydrocarbon or hydrocarbon derivative, exists, described method comprises makes described gaseous mixture and the step that the solid catalyst that Oxidation of Carbon Monoxide can be become carbonic acid gas under selected temperature contacts, and it is characterized in that described step carries out in fluidized-bed.
2. method as described in claim 1 is characterized in that described hydrocarbon is selected from and comprises the saturated of 2 to 6 carbon atoms or single-or the hydrocarbon of two undersaturated straight or brancheds, or comprise 6 to 12 carbon atoms can substituted aromatic hydrocarbons.
3. the method described in claim 1 or 2, it is characterized in that described hydrocarbon derivative is selected from acid anhydride, such as Tetra hydro Phthalic anhydride or maleic anhydride, aldehyde is such as propenal or Methylacrylaldehyde, unsaturated carboxylic acid, such as acrylic or methacrylic acid, unsaturated nitrile is such as vinyl cyanide, methacrylonitrile, atroponitrile, or their mixture, oxyethane, propylene oxide or 1,2-ethylene dichloride.
4. such as the method for claims 1 to 3 described in each, it is characterized in that described catalyzer is that granularity is 20 to 1000 microns, preferred 40 to 500 microns solids form.
5. as the method for aforementioned claim described in each, it is characterized in that described catalyzer is selected from based on loading on inorganic carrier, such as the precious metal on silicon-dioxide, titanium oxide, zirconium white, aluminum oxide, water glass or the silica, catalyzer such as platinum, palladium, rhodium or ruthenium, or based on copper, manganese, cobalt, nickel or iron, there is at least a precious metal with choosing wantonly, such as platinum, palladium, rhodium or ruthenium, for optionally supported at inorganic carrier, such as the catalyzer of the form of the mixed oxide on silicon-dioxide, titanium oxide, zirconium white, aluminum oxide, water glass or the silica or alloy.
6. corresponding temperature when the temperature that as the method for aforementioned claim described in each, it is characterized in that fluidized-bed is lower than oxidizing reaction with hydrocarbon and/or hydrocarbon derivative and begins.
7. as the method for aforementioned claim described in each, it is characterized in that the air speed SV that represents as hour volumetric flow rate with respect to the gaseous mixture of catalyst volume is 1000 h
-1To 30 000 h
-1
8. the manufacture method of hydrocarbon derivative, it comprises that at least one is with the step that is included in the fluidized-bed that Oxidation of Carbon Monoxide can be become the solid catalyst of carbonic acid gas under the selected temperature and comes the carbon monoxide that selective oxidation exists in the gaseous mixture that comprises at least a hydrocarbon or hydrocarbon derivative.
9. method as described in claim 8, it comprises at least the following step:
A) at least a hydrocarbon and oxygen or oxygen-containing gas are contacted with suitable catalyzer, comprise the gaseous mixture of at least a hydrocarbon derivative, unconverted hydrocarbon, oxygen and carbon monoxide with generation,
B) from from separating step reaction stream a) or extract hydrocarbon derivative,
C) then use to comprise and can under selected temperature, Oxidation of Carbon Monoxide be become the fluidized-bed of the solid catalyst of carbonic acid gas that the carbon monoxide that exists in the described air-flow is changed into carbonic acid gas, producing the gas stream of poor carbon monoxide,
D) gas stream with described poor carbon monoxide is recycled to reactions steps a).
10. the method described in claim 8 or 9 is characterized in that making in the selective permeation unit entering or leave step c) all or part of material flow through and separated, to remove at least a portion carbonic acid gas that in described material stream, exists.
11. the method described in claim 9 or 10 is characterized in that step a) carries out when existing for the heat town thing of inertia under the condition of the reaction of carrying out.
12. such as the method for claim 8 to 11 described in each, it is characterized in that described hydrocarbon is that propylene and described hydrocarbon derivative are vinylformic acid.
13. the method described in claim 11 or 12 is characterized in that using propane as heat town thing.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1052306A FR2958185B1 (en) | 2010-03-30 | 2010-03-30 | PROCESS FOR SELECTIVE OXIDATION OF CARBON MONOXIDE |
| FR1052306 | 2010-03-30 | ||
| PCT/FR2011/050692 WO2011124824A1 (en) | 2010-03-30 | 2011-03-29 | Process for the selective oxidation of carbon monoxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102906233A true CN102906233A (en) | 2013-01-30 |
Family
ID=42941861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800267977A Pending CN102906233A (en) | 2010-03-30 | 2011-03-29 | Process for selective oxidation of carbon monoxide |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US20130131380A1 (en) |
| EP (1) | EP2553056A1 (en) |
| JP (1) | JP5884128B2 (en) |
| KR (1) | KR20130080434A (en) |
| CN (1) | CN102906233A (en) |
| BR (1) | BR112012024627A2 (en) |
| FR (1) | FR2958185B1 (en) |
| SG (1) | SG184364A1 (en) |
| WO (1) | WO2011124824A1 (en) |
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|---|---|---|---|---|
| CN104128192A (en) * | 2014-07-14 | 2014-11-05 | 浙江工业大学 | CO low-temperature catalytic oxidation catalyst, and preparation method and application thereof |
| CN106542993A (en) * | 2015-09-17 | 2017-03-29 | 中国科学院大连化学物理研究所 | The oxidation of one step of propane prepares acrylic acid system and method |
| CN106715380A (en) * | 2014-10-07 | 2017-05-24 | Lg化学株式会社 | Method and apparatus for manufacturing continuous acrylic acid through propane partial oxidation reaction |
| CN107935836A (en) * | 2016-10-13 | 2018-04-20 | 中国科学院大连化学物理研究所 | CO selective oxidation removals method, one step oxidation of propane prepare acrylic acid and system |
| CN108212149A (en) * | 2017-04-22 | 2018-06-29 | 天津大学 | High dispersive type ruthenium oxide catalysts and its preparation method and application |
| CN110292929A (en) * | 2018-03-22 | 2019-10-01 | 中国科学院大连化学物理研究所 | CO selective oxidation removal catalyst and its preparation and application in a kind of recycled offgas |
| CN113617372A (en) * | 2021-09-13 | 2021-11-09 | 中冶长天国际工程有限责任公司 | High-dispersion CO oxidation catalyst and preparation method and application thereof |
| CN115340067A (en) * | 2022-08-29 | 2022-11-15 | 天津大学 | System and method for selective oxidation of CO using metal oxides |
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030228A (en) * | 1987-05-27 | 1989-01-11 | 日本触媒化学工业株式会社 | Produce acrylic acid |
| CN1062134A (en) * | 1990-10-31 | 1992-06-24 | 美国Boc氧气集团有限公司 | The production of hydrocarbon derivative |
| EP0495504A2 (en) * | 1991-01-17 | 1992-07-22 | Sumitomo Chemical Company, Limited | Process for production of methacrylic acid by catalytic oxidation of isobutane |
| CN1274343A (en) * | 1998-06-23 | 2000-11-22 | 潘托希米股份有限公司 | Process for prepn. of improved vanadium-phosphorus catalysts and use thereof for prodn. of maleic anhydride |
| CN1401429A (en) * | 2001-08-13 | 2003-03-12 | 中国科学院兰州化学物理研究所 | Combustible gas completely oxidizing catalyst |
| CN1428198A (en) * | 2001-12-25 | 2003-07-09 | 中国科学院大连化学物理研究所 | Noble metal catalyst for selective oxidation cleaning of micro CO in methanol reformed gas |
| EP1434833A2 (en) * | 2001-10-13 | 2004-07-07 | Johnson Matthey Public Limited Company | Selective oxidation |
| CN1579621A (en) * | 2003-08-06 | 2005-02-16 | 中国科学院兰州化学物理研究所 | Catalyst for removing carbon monoxide and its preparation method |
| CN101371985A (en) * | 2007-08-23 | 2009-02-25 | 中国石油化工股份有限公司 | Catalyst for removing trace amounts of CO as well as preparation method and use thereof |
| CN101507924A (en) * | 2007-12-17 | 2009-08-19 | 新日本石油株式会社 | Catalyst for oxidizing selectively carbon monoxide, method of reducing carbon monoxide concentration and fuel cell system |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE786398A (en) | 1971-07-21 | 1973-01-18 | Basf Ag | PROCESS FOR PREPARING ANHYDROUS ACRYLIC ACID |
| CA1041553A (en) * | 1973-07-30 | 1978-10-31 | John P. Longwell | Methanol and synthetic natural gas concurrent production |
| DE4308087C2 (en) | 1993-03-13 | 1997-02-06 | Basf Ag | Process for the separation of acrylic acid from the reaction gases of the catalytic oxidation of propylene and / or acrolein |
| US5907076A (en) * | 1996-12-31 | 1999-05-25 | Exxon Chemical Patents Inc. | Process for selectively separating hydrogen, or both hydrogen and carbon monoxide from olefinic hydrocarbons |
| US7524340B2 (en) * | 2001-07-11 | 2009-04-28 | May Walter R | Catalyst and method for improving combustion efficiency in engines, boilers, and other equipment operating on fuels |
| WO2004101136A2 (en) * | 2003-05-09 | 2004-11-25 | The Standard Oil Company | Fluidized bed reactor with gas cooler |
| MX2007015298A (en) * | 2005-06-01 | 2008-02-21 | Celanese Int Corp | Method for selectively oxidizing ethane to ethylene. |
| FR2897059B1 (en) * | 2006-02-07 | 2008-04-18 | Arkema Sa | PROCESS FOR THE PREPARATION OF ACRYLIC ACID |
-
2010
- 2010-03-30 FR FR1052306A patent/FR2958185B1/en not_active Expired - Fee Related
-
2011
- 2011-03-29 SG SG2012072641A patent/SG184364A1/en unknown
- 2011-03-29 US US13/638,682 patent/US20130131380A1/en not_active Abandoned
- 2011-03-29 BR BR112012024627A patent/BR112012024627A2/en not_active IP Right Cessation
- 2011-03-29 JP JP2013501910A patent/JP5884128B2/en not_active Expired - Fee Related
- 2011-03-29 WO PCT/FR2011/050692 patent/WO2011124824A1/en active Application Filing
- 2011-03-29 KR KR1020127028320A patent/KR20130080434A/en not_active Application Discontinuation
- 2011-03-29 EP EP11720137A patent/EP2553056A1/en not_active Withdrawn
- 2011-03-29 CN CN2011800267977A patent/CN102906233A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1030228A (en) * | 1987-05-27 | 1989-01-11 | 日本触媒化学工业株式会社 | Produce acrylic acid |
| CN1062134A (en) * | 1990-10-31 | 1992-06-24 | 美国Boc氧气集团有限公司 | The production of hydrocarbon derivative |
| EP0495504A2 (en) * | 1991-01-17 | 1992-07-22 | Sumitomo Chemical Company, Limited | Process for production of methacrylic acid by catalytic oxidation of isobutane |
| CN1274343A (en) * | 1998-06-23 | 2000-11-22 | 潘托希米股份有限公司 | Process for prepn. of improved vanadium-phosphorus catalysts and use thereof for prodn. of maleic anhydride |
| CN1401429A (en) * | 2001-08-13 | 2003-03-12 | 中国科学院兰州化学物理研究所 | Combustible gas completely oxidizing catalyst |
| EP1434833A2 (en) * | 2001-10-13 | 2004-07-07 | Johnson Matthey Public Limited Company | Selective oxidation |
| CN1428198A (en) * | 2001-12-25 | 2003-07-09 | 中国科学院大连化学物理研究所 | Noble metal catalyst for selective oxidation cleaning of micro CO in methanol reformed gas |
| CN1579621A (en) * | 2003-08-06 | 2005-02-16 | 中国科学院兰州化学物理研究所 | Catalyst for removing carbon monoxide and its preparation method |
| CN101371985A (en) * | 2007-08-23 | 2009-02-25 | 中国石油化工股份有限公司 | Catalyst for removing trace amounts of CO as well as preparation method and use thereof |
| CN101507924A (en) * | 2007-12-17 | 2009-08-19 | 新日本石油株式会社 | Catalyst for oxidizing selectively carbon monoxide, method of reducing carbon monoxide concentration and fuel cell system |
Non-Patent Citations (2)
| Title |
|---|
| M. P. LOBERA ET AL.: "Catalytic purification of H2-rich streams by CO-PROX over Pt-Co-Ce/γ-Al2O3 in fluidized bed reactors", 《CATALYSIS TODAY》, vol. 157, 26 February 2010 (2010-02-26) * |
| 王定锦: "《化学工程基础》", 31 October 1992, article "固定床与流化床催化反应器的比较" * |
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| CN104128192A (en) * | 2014-07-14 | 2014-11-05 | 浙江工业大学 | CO low-temperature catalytic oxidation catalyst, and preparation method and application thereof |
| CN104128192B (en) * | 2014-07-14 | 2016-04-13 | 浙江工业大学 | A kind of CO low-temperature catalytic oxidation Catalysts and its preparation method and application |
| CN106715380A (en) * | 2014-10-07 | 2017-05-24 | Lg化学株式会社 | Method and apparatus for manufacturing continuous acrylic acid through propane partial oxidation reaction |
| CN106542993A (en) * | 2015-09-17 | 2017-03-29 | 中国科学院大连化学物理研究所 | The oxidation of one step of propane prepares acrylic acid system and method |
| CN107935836A (en) * | 2016-10-13 | 2018-04-20 | 中国科学院大连化学物理研究所 | CO selective oxidation removals method, one step oxidation of propane prepare acrylic acid and system |
| CN107935836B (en) * | 2016-10-13 | 2021-01-22 | 中国科学院大连化学物理研究所 | CO selective oxidation removal method, method and system for preparing acrylic acid by one-step oxidation of propane |
| CN108212149A (en) * | 2017-04-22 | 2018-06-29 | 天津大学 | High dispersive type ruthenium oxide catalysts and its preparation method and application |
| CN110292929A (en) * | 2018-03-22 | 2019-10-01 | 中国科学院大连化学物理研究所 | CO selective oxidation removal catalyst and its preparation and application in a kind of recycled offgas |
| CN113617372A (en) * | 2021-09-13 | 2021-11-09 | 中冶长天国际工程有限责任公司 | High-dispersion CO oxidation catalyst and preparation method and application thereof |
| CN113617372B (en) * | 2021-09-13 | 2023-10-27 | 中冶长天国际工程有限责任公司 | High-dispersion CO oxidation catalyst and preparation method and application thereof |
| CN115340067A (en) * | 2022-08-29 | 2022-11-15 | 天津大学 | System and method for selective oxidation of CO using metal oxides |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2011124824A1 (en) | 2011-10-13 |
| SG184364A1 (en) | 2012-11-29 |
| BR112012024627A2 (en) | 2016-05-31 |
| EP2553056A1 (en) | 2013-02-06 |
| JP2013523432A (en) | 2013-06-17 |
| FR2958185A1 (en) | 2011-10-07 |
| JP5884128B2 (en) | 2016-03-15 |
| US20130131380A1 (en) | 2013-05-23 |
| FR2958185B1 (en) | 2012-04-20 |
| KR20130080434A (en) | 2013-07-12 |
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